Process of separating gases using polyimide membranes

ABSTRACT

The present invention discloses a new type of polyimide membrane with high permeances and high selectivities for gas separations and particularly for CO 2 /CH 4  and H 2 /CH 4  separations. The polyimide membranes have CO 2  permeability of 50 Barrers or higher and single-gas selectivity for CO 2 /CH 4  of 15 or higher at 50° C. under 791 kPa for CO 2 /CH 4  separation. The polyimide membranes have UV cross-linkable functional groups and can be used for the preparation of UV cross-linked polyimide membranes having CO 2  permeability of 20 Barrers or higher and single-gas selectivity for CO 2 /CH 4  of 35 or higher at 50° C. under 791 kPa for CO 2 /CH 4  separation.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.61/498,116 filed Jun. 17, 2011, the contents of which are herebyincorporated by reference.

BACKGROUND OF THE INVENTION

This invention relates to a new type of polyimide membrane with highpermeances and high selectivities for gas separations and moreparticularly for use in natural gas upgrading and hydrogen purification.

In the past 30-35 years, the state of the art of polymer membrane-basedgas separation processes has evolved rapidly. Membrane-basedtechnologies are a low capital cost solution and provide high energyefficiency compared to conventional separation methods. Membrane gasseparation is of special interest to petroleum producers and refiners,chemical companies, and industrial gas suppliers. Several applicationsof membrane gas separation have achieved commercial success, includingN₂ enrichment from air, carbon dioxide removal from natural gas and fromenhanced oil recovery, and also in hydrogen removal from nitrogen,methane, and argon in ammonia purge gas streams. For example, UOP'sSeparex™ cellulose acetate spiral wound polymeric membrane is currentlyan international market leader for carbon dioxide removal from naturalgas.

Polymers provide a range of properties including low cost, permeability,mechanical stability, and ease of processability that are important forgas separation. Glassy polymers (i.e., polymers at temperatures belowtheir T_(g)) have stiffer polymer backbones and therefore allow smallermolecules such as hydrogen and helium pass through more quickly, whilelarger molecules such as hydrocarbons pass through more slowly ascompared to polymers with less stiff backbones. Cellulose acetate (CA)glassy polymer membranes are used extensively in gas separation.Currently, such CA membranes are used for natural gas upgrading,including the removal of carbon dioxide. Although CA membranes have manyadvantages, they are limited in a number of properties includingselectivity, permeability, and in chemical, thermal, and mechanicalstability. High performance polymers such as polyimides (PIs),poly(trimethylsilylpropyne), and polytriazole have been developed toimprove membrane selectivity, permeability, and thermal stability. Thesepolymeric membrane materials have shown promising intrinsic propertiesfor separation of gas pairs such as CO₂/CH₄, O₂/N₂, H₂/CH₄, andpropylene/propane (C₃H₆/C₃H₈).

The membranes most commonly used in commercial gas and liquid separationapplications are asymmetric polymeric membranes and have a thinnonporous selective skin layer that performs the separation. Separationis based on a solution-diffusion mechanism. This mechanism involvesmolecular-scale interactions of the permeating gas with the membranepolymer. The mechanism assumes that in a membrane having two opposingsurfaces, each component is sorbed by the membrane at one surface,transported by a gas concentration gradient, and desorbed at theopposing surface. According to this solution-diffusion model, themembrane performance in separating a given pair of gases (e.g., CO₂/CH₄,O₂/N₂, H₂/CH₄) is determined by two parameters: the permeabilitycoefficient (abbreviated hereinafter as permeability or P_(A)) and theselectivity (α_(A/B)). The P_(A) is the product of the gas flux and theselective skin layer thickness of the membrane, divided by the pressuredifference across the membrane. The α_(A/B) is the ratio of thepermeability coefficients of the two gases (α_(A/B)=P_(A)/P_(B)) whereP_(A) is the permeability of the more permeable gas and P_(B) is thepermeability of the less permeable gas. Gases can have high permeabilitycoefficients because of a high solubility coefficient, a high diffusioncoefficient, or because both coefficients are high. In general, thediffusion coefficient decreases while the solubility coefficientincreases with an increase in the molecular size of the gas. In highperformance polymer membranes, both high permeability and selectivityare desirable because higher permeability decreases the size of themembrane area required to treat a given volume of gas, therebydecreasing capital cost of membrane units, and because higherselectivity results in a higher purity product gas.

One of the components to be separated by a membrane must have asufficiently high permeance at the preferred conditions or anextraordinarily large membrane surface area is required to allowseparation of large amounts of material. Permeance, measured in GasPermeation Units (GPU, 1 GPU=10⁻⁶ cm³ (STP)/cm² s (cm Hg)), is thepressure normalized flux and equals to permeability divided by the skinlayer thickness of the membrane. Commercially available gas separationpolymer membranes, such as CA, polyimide, and polysulfone membranesformed by phase inversion and solvent exchange methods have anasymmetric integrally skinned membrane structure. Such membranes arecharacterized by a thin, dense, selectively semipermeable surface “skin”and a less dense void-containing (or porous), non-selective supportregion, with pore sizes ranging from large in the support region to verysmall proximate to the “skin”. However, it is very complicated andtedious to make such asymmetric integrally skinned membranes having adefect-free skin layer. The presence of nanopores or defects in the skinlayer reduces the membrane selectivity. Another type of commerciallyavailable gas separation polymer membrane is the thin film composite (orTFC) membrane, comprising a thin selective skin deposited on a poroussupport. TFC membranes can be formed from CA, polysulfone,polyethersulfone, polyamide, polyimide, polyetherimide, cellulosenitrate, polyurethane, polycarbonate, polystyrene, etc. Fabrication ofTFC membranes that are defect-free is also difficult, and requiresmultiple steps. Yet another approach to reduce or eliminate thenanopores or defects in the skin layer of the asymmetric membranes hasbeen the fabrication of an asymmetric membrane comprising a relativelyporous and substantial void-containing selective “parent” membrane suchas polysulfone or cellulose acetate that would have high selectivitywere it not porous, in which the parent membrane is coated with amaterial such as a polysiloxane, a silicone rubber, or a UV-curableepoxysilicone in occluding contact with the porous parent membrane, thecoating filling surface pores and other imperfections comprising voids.The coating of such coated membranes, however, is subject to swelling bysolvents, poor performance durability, low resistance to hydrocarboncontaminants, and low resistance to plasticization by the sorbedpenetrant molecules such as CO₂ or C₃H₆.

Many of the deficiencies of these prior art membranes are improved inthe present invention which provides a new type of polyimide membranewith high permeances and high selectivities for gas separations.

SUMMARY OF THE INVENTION

A new type of polyimide membrane with high permeances and highselectivities for gas separations has been made.

The present invention generally relates to gas separation membranes and,more particularly, to high permeance and high selectivity polyimidemembranes for gas separations. The polyimide membranes with highpermeances and high selectivities described in the current inventionhave CO₂ permeability at least 50 Barrer (1 Barrer=10⁻¹⁰ cm³ (STP)cm/cm² s (cm Hg)) and single-gas CO₂/CH₄ selectivity at least 15 at 50°C. under 791 kPa feed pressure.

The present invention provides a new type of polyimide membranes withhigh permeance and high selectivity for gas separations. One polyimidemembrane described in the present invention is fabricated frompoly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine) polyimide (abbreviatedas NPI-1), which is derived from the polycondensation reaction of3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) with2,4,6-trimethyl-m-phenylenediamine (TMPDA). Tests showed that this NPI-1polyimide membrane has an intrinsic CO₂ permeability of 73.4 Barrers andsingle-gas CO₂/CH₄ selectivity of 25.3 at 50° C. under 791 kPa forCO₂/CH₄ separation. This membrane also has intrinsic H₂ permeability of136.6 Barrers and single-gas H₂/CH₄ selectivity of 47.1 at 50° C. under791 kPa for H₂/CH₄ separation. This NPI-1 polyimide membrane contains UVcross-linkable sulfonic groups.

Another polyimide membrane described in the present invention isfabricated from poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-3,3′,4,4′-biphenyl tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimide (abbreviated as NPI-2), which is derived from thepolycondensation reaction of DSDA and 3,3′,4,4′-biphenyl tetracarboxylicdianhydride (BPDA) with 3,3′,5,5′-tetramethyl-4,4′-methylene dianiline(TMMDA) and TMPDA (DSDA:BPDA:TMMDA:TMPDA=3.06:1.02:2.00:2.00 (molarratio)). Pure gas permeation results showed that this NPI-2 membrane hasan intrinsic CO₂ permeability of 57.5 Barrers and single-gas CO₂/CH₄selectivity of 20.2 at 50° C. under 791 kPa for CO₂/CH₄ separation. Thismembrane also has intrinsic H₂ permeability of 109.9 Barrers andsingle-gas H₂/CH₄ selectivity of 38.6 at 50° C. under 791 kPa for H₂/CH₄separation. This NPI-2 membrane contains UV cross-linkable sulfonicgroups.

Yet another polyimide membrane that is a part of the present inventionis fabricated from poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromellitic dianhydride-2,4,6-trimethyl-m-phenylenediamine)polyimide (abbreviated as NPI-3), which is derived from thepolycondensation reaction of 3,3′,4,4′-benzophenone tetracarboxylicdianhydride (BTDA) and pyromellitic dianhydride (PMDA) with TMPDA(BTDA:PMDA:TMPDA=2.04:2.04:4.00 (molar ratio)). Pure gas permeationresults showed that this NPI-3 membrane has an intrinsic CO₂permeability of 179 Barrers and single-gas CO₂/CH₄ selectivity of 15.8at 50° C. under 791 kPa for CO₂/CH₄ separation. This membrane also hasintrinsic H₂ permeability of 256.5 Barrers and single-gas H₂/CH₄selectivity of 22.7 at 50° C. under 791 kPa for H₂/CH₄ separation. ThisNPI-3 membrane contains UV cross-linkable carbonyl groups.

Yet another polyimide membrane that is a part of the present inventionis fabricated from poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromelliticdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimide (abbreviated as NPI-4), which is derived from thepolycondensation reaction of BTDA and PMDA with TMPDA and TMMDA(BTDA:PMDA:TMPDA:TMMDA=2.04:2.04:2.00:2.00 (molar ratio)). Pure gaspermeation results showed that this NPI-4 membrane has an intrinsic CO₂permeability of 97.0 Barrers and single-gas CO₂/CH₄ selectivity of 17.1at 50° C. under 791 kPa for CO₂/CH₄ separation. This membrane also hasintrinsic H₂ permeability of 159.5 Barrers and single-gas H₂/CH₄selectivity of 28.2 at 50° C. under 791 kPa for H₂/CH₄ separation. ThisNPI-4 membrane contains UV cross-linkable carbonyl groups.

In another embodiment of the invention, this invention pertains to highperformance polyimide membranes that have undergone an additionalcrosslinking step, by chemical or UV crosslinking or other crosslinkingprocess as known to one skilled in the art. A cross-linked polyimidemembrane can be prepared by UV cross-linking of the polyimide membranevia exposure of the membrane to UV radiation. The polyimide polymersused for the preparation of the polyimide membranes described in thecurrent invention have UV cross-linkable sulfonic (—SO₂—) or carbonyl(—C(O)—) functional groups. The cross-linked polyimide membranescomprise polymer chain segments where at least part of these polymerchain segments are cross-linked to each other through possible directcovalent bonds by exposure to UV radiation. The cross-linking of thepolyimide membranes provides the membranes with improved selectivitiesand decreased permeances compared to the corresponding uncross-linkedpolyimide membranes.

The membrane dope formulation for the preparation of polyimide membraneswith high permeances for gas separations in the present inventioncomprises N-methylpyrrolidone (NMP) and 1,3-dioxolane which are goodsolvents for the polyimide polymer. In some cases, the membrane dopeformulation for the preparation of polyimide membranes with highpermeances and high selectivities for gas separations in the presentinvention also comprises acetone and isopropanol (or methanol) which arepoor solvents for the polyimide polymer. The new polyimide membraneswith high permeances and high selectivities for gas separationsdescribed in the current invention have either flat sheet (spiral wound)or hollow fiber geometry. In some cases, the selective skin layersurface of the polyimide membranes is coated with a thin layer ofmaterial such as a polysiloxane, a fluoropolymer, a thermally curablesilicone rubber, or a UV radiation cured silicone rubber.

The invention provides a process for separating at least one gas from amixture of gases using the new polyimide membranes with high permeancesand high selectivities described herein, the process comprising: (a)providing a polyimide membrane with high permeance and high selectivitydescribed in the present invention which is permeable to said at leastone gas; (b) contacting the mixture on one side of the polyimidemembrane to cause said at least one gas to permeate the membrane; and(c) removing from the opposite side of the membrane a permeate gascomposition comprising a portion of said at least one gas whichpermeated said membrane.

The new polyimide membranes with high permeances and high selectivitiesare not only suitable for a variety of liquid, gas, and vaporseparations such as desalination of water by reverse osmosis,non-aqueous liquid separation such as deep desulfurization of gasolineand diesel fuels, ethanol/water separations, pervaporation dehydrationof aqueous/organic mixtures, CO₂/CH₄, CO₂/N₂, H₂/CH₄, O₂/N₂, H₂S/CH₄,olefin/paraffin, iso/normal paraffins separations, and other light gasmixture separations, but also can be used for other applications such asfor catalysis and fuel cell applications.

DETAILED DESCRIPTION OF THE INVENTION

The use of membranes for separation of both gases and liquids is agrowing technological area with potentially high economic reward due tothe low energy requirements and the potential for scaling up of modularmembrane designs. Advances in membrane technology, with the continuingdevelopment of new membrane materials and new methods for the productionof high performance membranes will make this technology even morecompetitive with traditional, high-energy intensive and costly processessuch as distillation. Among the applications for large scale gasseparation membrane systems are nitrogen enrichment, oxygen enrichment,hydrogen recovery, removal of hydrogen sulfide and carbon dioxide fromnatural gas and dehydration of air and natural gas. Various hydrocarbonseparations are potential applications for the appropriate membranesystem. The membranes that are used in these applications must have highselectivity, durability, and productivity in processing large volumes ofgas or liquid in order to be economically successful. Membranes for gasseparations have evolved rapidly in the past 25 years due to their easyprocessability for scale-up and low energy requirements. More than 90%of the membrane gas separation applications involve the separation ofnoncondensable gases such as carbon dioxide from methane, nitrogen fromair, and hydrogen from nitrogen, argon or methane. Membrane gasseparation is of special interest to petroleum producers and refiners,chemical companies, and industrial gas suppliers. Several applicationsof membrane gas separation have achieved commercial success, includingnitrogen enrichment from air, carbon dioxide removal from natural gasand biogas and in enhanced oil recovery.

The present invention provides a new type of polyimide membranes withhigh permeances and high selectivities for gas separations. Thisinvention also pertains to the application of these polyimide membraneswith high permeances and high selectivities for a variety of gasseparations such as separations of CO₂/CH₄, H₂S/CH₄, CO₂/N₂,olefin/paraffin separations (e.g. propylene/propane separation), H₂/CH₄,O₂/N₂, iso/normal paraffins, polar molecules such as H₂O, H₂S, andNH₃/mixtures with CH₄, N₂, H₂, and other light gases separations, aswell as for liquid separations such as desalination and pervaporation.

The membrane dope formulation for the preparation of polyimide membraneswith high permeances and high selectivities for gas separations in thepresent invention comprises good solvents for the polyimide polymer thatcan completely dissolve the polymer. Representative good solvents foruse in this invention include N-methylpyrrolidone (NMP), N,N-dimethylacetamide (DMAC), methylene chloride, N,N-dimethylformamide (DMF),dimethyl sulfoxide (DMSO), dioxanes, 1,3-dioxolane, mixtures thereof,others known to those skilled in the art and mixtures thereof. In somecases, the membrane dope formulation for the preparation of polyimidemembranes with high permeances and high selectivities for gasseparations in the present invention also comprises poor solvents forthe polyimide polymer that cannot dissolve the polymer such as acetone,methanol, ethanol, tetrahydrofuran (THF), toluene, n-octane, n-decane,lactic acid, citric acid, isopropanol, and mixtures thereof. It isbelieved that the proper weight ratio of the solvents used in thepresent invention provides asymmetric polyimide membranes with <100 nmsuper thin nonporous selective skin layer which results in highpermeances. The polyimide membranes with high permeances and highselectivities described in the present invention have CO₂ permeabilityof at least 50 Barrers and single-gas CO₂/CH₄ selectivity at least 15 at50° C. under 791 kPa feed pressure.

The present invention provides a new type of polyimide membranes withhigh permeances and high selectivities for gas separations. Onepolyimide membrane described in the present invention is fabricated frompoly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine) polyimide (abbreviatedas NPI-1), which is derived from the polycondensation reaction of3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) with2,4,6-trimethyl-m-phenylenediamine (TMPDA). Tests showed that this NPI-1polyimide membrane has an intrinsic CO₂ permeability of 73.4 Barrers andsingle-gas CO₂/CH₄ selectivity of 25.3 at 50° C. under 791 kPa forCO₂/CH₄ separation. This membrane also has intrinsic H₂ permeability of136.6 Barrers and single-gas H₂/CH₄ selectivity of 47.1 at 50° C. under791 kPa for H₂/CH₄ separation. This NPI-1 polyimide membrane contains UVcross-linkable sulfonic groups.

Another polyimide membrane described in the present invention isfabricated from poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-3,3′,4,4′-biphenyl tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimide (abbreviated as NPI-2), which is derived from thepolycondensation reaction of DSDA and 3,3′,4,4′-biphenyl tetracarboxylicdianhydride (BPDA) with 3,3′,5,5′-tetramethyl-4,4′-methylene dianiline(TMMDA) and TMPDA (DSDA:BPDA:TMMDA:TMPDA=3.06:1.02:2.00:2.00 (molarratio)). Pure gas permeation results showed that this NPI-2 membrane hasan intrinsic CO₂ permeability of 57.5 Barrers and single-gas CO₂/CH₄selectivity of 20.2 at 50° C. under 791 kPa for CO₂/CH₄ separation. Thismembrane also has intrinsic H₂ permeability of 109.9 Barrers andsingle-gas H₂/CH₄ selectivity of 38.6 at 50° C. under 791 kPa for H₂/CH₄separation. This NPI-2 membrane contains UV cross-linkable sulfonicgroups.

Yet another polyimide membrane that is a part of the present inventionis fabricated from poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromellitic dianhydride-2,4,6-trimethyl-m-phenylenediamine)polyimide (abbreviated as NPI-3), which is derived from thepolycondensation reaction of 3,3′,4,4′-benzophenone tetracarboxylicdianhydride (BTDA) and pyromellitic dianhydride (PMDA) with TMPDA(BTDA:PMDA:TMPDA=2.04:2.04:4.00 (molar ratio)). Pure gas permeationresults showed that this NPI-3 membrane has an intrinsic CO₂permeability of 179 Barrers and single-gas CO₂/CH₄ selectivity of 15.8at 50° C. under 791 kPa for CO₂/CH₄ separation. This membrane also hasintrinsic H₂ permeability of 256.5 Barrers and single-gas H₂/CH₄selectivity of 22.7 at 50° C. under 791 kPa for H₂/CH₄ separation. ThisNPI-3 membrane contains UV cross-linkable carbonyl groups.

Yet another polyimide membrane that is a part of the present inventionis fabricated from poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromelliticdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimide (abbreviated as NPI-4), which is derived from thepolycondensation reaction of BTDA and PMDA with TMPDA and TMMDA(BTDA:PMDA:TMPDA:TMMDA=2.04:2.04:2.00:2.00 (molar ratio)). Pure gaspermeation results showed that this NPI-4 membrane has an intrinsic CO₂permeability of 97.0 Barrers and single-gas CO₂/CH₄ selectivity of 17.1at 50° C. under 791 kPa for CO₂/CH₄ separation. This membrane also hasintrinsic H₂ permeability of 159.5 Barrers and single-gas H₂/CH₄selectivity of 28.2 at 50° C. under 791 kPa for H₂/CH₄ separation. ThisNPI-4 membrane contains UV cross-linkable carbonyl groups.

In some cases, the high performance polyimide membranes described in thepresent invention have undergone an additional crosslinking step, bychemical or UV crosslinking or other crosslinking process as known toone skilled in the art. A cross-linked polyimide membrane can beprepared by UV cross-linking of the polyimide membrane via exposure ofthe membrane to UV radiation. The polyimide polymers used for thepreparation of the polyimide membranes described in the currentinvention have UV cross-linkable sulfonic (—SO₂—) or carbonyl (—C(O)—)functional groups. The cross-linked polyimide membranes comprise polymerchain segments where at least part of these polymer chain segments arecross-linked to each other through possible direct covalent bonds byexposure to UV radiation. The cross-linking of the polyimide membranesprovides the membranes with improved selectivities and decreasedpermeances compared to the corresponding uncross-linked polyimidemembranes. The UV cross-linked polyimide membranes described in thecurrent invention have CO₂ permeability of 20 Barrers or higher andsingle-gas selectivity for CO₂/CH₄ of 35 or higher at 50° C. under 791kPa for CO₂/CH₄ separation.

Optimization of the cross-linking degree in the UV cross-linkedpolyimide membrane described in the present invention should promote thetailoring of membranes for a wide range of gas and liquid separationswith improved permeation properties and environmental stability. Thecross-linking degree of the UV-cross-linked polyimide membranes of thepresent invention can be controlled by adjusting the distance betweenthe UV lamp and the membrane surface, UV radiation time, wavelength andstrength of UV light, etc. Preferably, the distance from the UV lamp tothe membrane surface is in the range of 0.8 to 25.4 cm (0.3 to 10inches) with a UV light provided from 12 watt to 450 watt low pressureor medium pressure mercury arc lamp, and the UV radiation time is in therange of 0.5 min to 1 h. More preferably, the distance from the UV lampto the membrane surface is in the range of 1.3 to 5.1 cm (0.5 to 2inches) with a UV light provided from 12 watt to 450 watt low pressureor medium pressure mercury arc lamp, and the UV radiation time is in therange of 1 to 40 minutes.

As an example, UV cross-linked NPI-4 membrane is prepared by further UVcross-linking the UV cross-linkable NPI-4 membrane using a UV lamp froma certain distance and for a period of time selected based upon theseparation properties sought. For example, UV cross-linked NPI-4membrane can be prepared from NPI-4 membrane by exposure to UV radiationusing 254 nm wavelength UV light generated from a UV lamp with 1.9 cm(0.75 inch) distance from the membrane surface to the UV lamp and aradiation time of 10 min at 50° C. The UV lamp described here is a lowpressure, mercury arc immersion UV quartz 12 watt lamp with 12 wattpower supply from Ace Glass Incorporated. Pure gas permeation resultsshowed that the UV cross-linked NPI-4 membrane has an intrinsic CO₂permeability of 39.3 Barrers and single-gas CO₂/CH₄ selectivity of 41.2at 50° C. under 791 kPa for CO₂/CH₄ separation. This UV cross-linkedNPI-4 membrane also has intrinsic H₂ permeability of 149.8 Barrers andsingle-gas H₂/CH₄ selectivity of 156.8 at 50° C. under 791 kPa forH₂/CH₄ separation. These results indicate that the UV cross-linked NPI-4membrane has significantly enhanced single-gas CO₂/CH₄ selectivity andsingle-gas H₂/CH₄ selectivity compared to the uncross-linked NPI-4membrane.

The polyimide polymers used for making the polyimide membranes with highpermeances and high selectivities described in the current invention maycomprise a plurality of first repeating units of formula (I):

wherein X1 is selected from the group consisting of

and mixtures thereof. X2 is selected from the group consisting of

and mixtures thereof. Y is selected from the group consisting of

and mixtures thereof and n and m are independent integers from 2 to 500.

The polyimide polymers used for making the polyimide membranes with highpermeances and high selectivities described in the current inventionhave a weight average molecular weight in the range of 50,000 to1,000,000 Daltons, preferably between 70,000 to 500,000 Daltons.

Some examples of polyimide polymers used for making the polyimidemembranes with high permeances and high selectivities described in thecurrent invention may include, but are not limited to:poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine) polyimide (abbreviatedas NPI-1) derived from the polycondensation reaction of3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) with2,4,6-trimethyl-m-phenylenediamine (TMPDA);poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-3,3′,4,4′-biphenyl tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimides derived from the polycondensation reaction of DSDAand 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) with3,3′,5,5′-tetramethyl-4,4′-methylene dianiline (TMMDA) and TMPDA(abbreviated as NPI-2 when DSDA:BPDA:TMMDA:TMPDA=3.06:1.02:2.00:2.00(molar ratio) and abbreviated as NPI-5 whenDSDA:BPDA:TMMDA:TMPDA=2.04:2.04:1.00:3.00 (molar ratio));poly(3,3′,4,4′-benzophenone tetracarboxylic dianhydride-pyromelliticdianhydride-2,4,6-trimethyl-m-phenylenediamine) polyimides derived fromthe polycondensation reaction of 3,3′,4,4′-benzophenone tetracarboxylicdianhydride (BTDA) and pyromellitic dianhydride (PMDA) with TMPDA(abbreviated as NPI-3 when BTDA:PMDA:TMPDA=2.04:2.04:4.00 (molar ratio)and abbreviated as NPI-6 when BTDA:PMDA:TMPDA=2.45:1.63:4.00 (molarratio)); poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromelliticdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) polyimide (abbreviated as NPI-4) derived from thepolycondensation reaction of BTDA and PMDA with TMPDA and TMMDA(BTDA:PMDA:TMPDA:TMMDA=2.04:2.04:2.00:2.00 (molar ratio)).

The polyimide membranes described in the present invention can befabricated into any convenient geometry such as flat sheet (or spiralwound), tube, or hollow fiber.

The present invention also involves blend polymer membranes comprisingthe polyimide polymers used for making the polyimide membranes with highpermeances and high selectivities described in the current invention. Insome embodiments of the invention, the blend polymer membranescomprising the polyimide polymers used for making the polyimidemembranes with high permeances and high selectivities described in thecurrent invention may be subjected to an additional crosslinking step toincrease the selectivity of the membrane.

The term “blend polymer membrane” in the present invention refers to amembrane prepared from a blend of two or more polymers. The blendpolymer membrane comprising the polyimide polymers used for making thepolyimide membranes with high permeances and high selectivitiesdescribed in the current invention contains a blend of two or morepolymers wherein at least one polymer is a polyimide polymer describedin the present invention.

In some cases, it is desirable to cross-link the blend polymer membraneto improve the membrane selectivity. The cross-linked blend polymermembrane described in the current invention is prepared by UVcross-linking of the blend polymer membrane comprising at least onepolyimide polymer used for making the polyimide membranes with highpermeances and high selectivities described in the current invention.After UV cross-linking, the cross-linked blend polymer membranecomprises polymer chain segments wherein at least part of these polymerchain segments are cross-linked to each other through possible directcovalent bonds by exposure to UV radiation. The cross-linking of theblend polymer membranes offers the membranes superior selectivity andimproved chemical and thermal stabilities than the correspondinguncross-linked blend polymer membranes comprising at least one polyimidepolymer used for making the polyimide membranes with high permeances andhigh selectivities described in the current invention.

The second polymer in the blend polymer membrane comprising thepolyimide polymers described in the current invention can be selectedfrom, but is not limited to, polysulfones; sulfonated polysulfones;polyethersulfones; sulfonated polyethersulfones; andpolyvinylpyrrolidones. The invention provides a process for separatingat least one gas from a mixture of gases using the new polyimidemembranes with high permeances and high selectivities described in thepresent invention, the process comprising: (a) providing a polyimidemembrane with high permeance and high selectivity described in thepresent invention which is permeable to the at least one gas; (b)contacting the mixture on one side of the asymmetric polyimide membranewith high permeance described in the present invention to cause the atleast one gas to permeate the membrane; and (c) removing from theopposite side of the membrane a permeate gas composition comprising aportion of the at least one gas which permeated the asymmetric polyimidemembrane.

The polyimide membranes with high permeances and high selectivitiesdescribed in the present invention are especially useful in thepurification, separation or adsorption of a particular species in theliquid or gas phase. In addition to separation of pairs of gases, thesepolyimide membranes with high permeances and high selectivitiesdescribed in the present invention may, for example, be used for thedesalination of water by reverse osmosis or for the separation ofproteins or other thermally unstable compounds, e.g. in thepharmaceutical and biotechnology industries. The polyimide membraneswith high permeances and high selectivities described in the presentinvention may also be used in fermenters and bioreactors to transportgases into the reaction vessel and transfer cell culture medium out ofthe vessel. Additionally, these polyimide membranes with high permeancesand high selectivities described in the present invention may be usedfor the removal of microorganisms from air or water streams, waterpurification, and ethanol production in a continuousfermentation/membrane pervaporation system, and in detection or removalof trace compounds or metal salts in air or water streams.

The polyimide membranes with high permeances and high selectivitiesdescribed in the present invention are especially useful in gasseparation processes in air purification, petrochemical, refinery, andnatural gas industries. Examples of such separations include separationof volatile organic compounds (such as toluene, xylene, and acetone)from an atmospheric gas, such as nitrogen or oxygen and nitrogenrecovery from air. Further examples of such separations are for theseparation of CO₂ or H₂S from natural gas, H₂ from N₂, CH₄, and Ar inammonia purge gas streams, H₂ recovery in refineries, olefin/paraffinseparations such as propylene/propane separation, and iso/normalparaffin separations. Any given pair or group of gases that differ inmolecular size, for example nitrogen and oxygen, carbon dioxide andmethane, hydrogen and methane or carbon monoxide, helium and methane,can be separated using the polyimide membranes with high permeancesdescribed in the present invention. More than two gases can be removedfrom a third gas. For example, some of the gas components which can beselectively removed from a raw natural gas using the membrane describedherein include carbon dioxide, oxygen, nitrogen, water vapor, hydrogensulfide, helium, and other trace gases. Some of the gas components thatcan be selectively retained include hydrocarbon gases. When permeablecomponents are acid components selected from the group consisting ofcarbon dioxide, hydrogen sulfide, and mixtures thereof and are removedfrom a hydrocarbon mixture such as natural gas, one module, or at leasttwo in parallel service, or a series of modules may be utilized toremove the acid components. For example, when one module is utilized,the pressure of the feed gas may vary from 275 kPa to about 7.5 MPa (25to 4000 psig). The differential pressure across the membrane can be aslow as about 70 kPa or as high as 14.5 MPa (about 10 psi or as high asabout 2100 psi) depending on many factors such as the particularmembrane used, the flow rate of the inlet stream and the availability ofa compressor to compress the permeate stream if such compression isdesired. Differential pressure greater than about 14.5 MPa (2100 psi)may rupture the membrane. A differential pressure of at least 0.7 MPa(100 psi) is preferred since lower differential pressures may requiremore modules, more time and compression of intermediate product streams.The operating temperature of the process may vary depending upon thetemperature of the feed stream and upon ambient temperature conditions.Preferably, the effective operating temperature of the membranes of thepresent invention will range from about −50° to about 150° C. Morepreferably, the effective operating temperature of the polyimidemembranes with high permeances of the present invention will range fromabout −20° to about 100° C., and most preferably, the effectiveoperating temperature of the membranes of the present invention willrange from about 25° to about 100° C.

The polyimide membranes with high permeances and high selectivitiesdescribed in the present invention are also especially useful ingas/vapor separation processes in chemical, petrochemical,pharmaceutical and allied industries for removing organic vapors fromgas streams, e.g. in off-gas treatment for recovery of volatile organiccompounds to meet clean air regulations, or within process streams inproduction plants so that valuable compounds (e.g., vinylchloridemonomer, propylene) may be recovered. Further examples of gas/vaporseparation processes in which polyimide membranes with high permeancesand high selectivities and described in the present invention may beused are hydrocarbon vapor separation from hydrogen in oil and gasrefineries, for hydrocarbon dew pointing of natural gas (i.e. todecrease the hydrocarbon dew point to below the lowest possible exportpipeline temperature so that liquid hydrocarbons do not separate in thepipeline), for control of methane number in fuel gas for gas engines andgas turbines, and for gasoline recovery. The polyimide membranes withhigh permeances and high selectivities described in the presentinvention may incorporate a species that adsorbs strongly to certaingases (e.g. cobalt porphyrins or phthalocyanines for O₂ or silver (I)for ethane) to facilitate their transport across the membrane.

The polyimide membranes with high permeances and high selectivitiesdescribed in the present invention also have immediate application toconcentration of olefins in a paraffin/olefin stream for an olefincracking application. For example, the polyimide membranes with highpermeances and high selectivities described in the present invention canbe used for propylene/propane separation to increase the concentrationof the effluent in a catalytic dehydrogenation reaction for theproduction of propylene from propane and isobutylene from isobutane.Therefore, the number of stages of a propylene/propane splitter that isrequired to get polymer grade propylene can be reduced. Anotherapplication for the polyimide membranes with high permeances and highselectivities described in the present invention is for separatingisoparaffin and normal paraffin in light paraffin isomerization andMaxEne™, a process for enhancing the concentration of normal paraffin(n-paraffin) in the naphtha cracker feedstock, which can be thenconverted to ethylene.

The polyimide membranes with high permeances and high selectivitiesdescribed in the present invention can also be operated at hightemperature to provide the sufficient dew point margin for natural gasupgrading (e.g, CO₂ removal from natural gas). The polyimide membraneswith high permeances and high selectivities described in the presentinvention can be used in either a single stage membrane or as the firstor/and second stage membrane in a two stage membrane system for naturalgas upgrading. The polyimide membranes with high permeances and highselectivities described in the present invention have high selectivity,high permeance, high mechanical stability, and high thermal and chemicalstabilities that allow the membranes to be operated without a costlypretreatment system. Due to the elimination of the pretreatment systemand the significant reduction of membrane area, the new process canachieve significant capital cost saving and reduce the existing membranefootprint.

These polyimide membranes with high permeances and high selectivitiesdescribed in the present invention may also be used in the separation ofliquid mixtures by pervaporation, such as in the removal of organiccompounds (e.g., alcohols, phenols, chlorinated hydrocarbons, pyridines,ketones) from water such as aqueous effluents or process fluids. Amembrane which is ethanol-selective would be used to increase theethanol concentration in relatively dilute ethanol solutions (5-10%ethanol) obtained by fermentation processes. Another liquid phaseseparation example using these polyimide membranes with high permeancesand high selectivities described in the present invention is the deepdesulfurization of gasoline and diesel fuels by a pervaporation membraneprocess similar to the process described in U.S. Pat. No. 7,048,846,incorporated by reference herein in its entirety. The polyimidemembranes with high permeances and high selectivities described in thepresent invention that are selective to sulfur-containing moleculeswould be used to selectively remove sulfur-containing molecules fromfluid catalytic cracking (FCC) and other naphtha hydrocarbon streams.Further liquid phase examples include the separation of one organiccomponent from another organic component, e.g. to separate isomers oforganic compounds. Mixtures of organic compounds which may be separatedusing polyimide membranes with high permeances described in the presentinvention include: ethylacetate-ethanol, diethylether-ethanol, aceticacid-ethanol, benzene-ethanol, chloroform-ethanol, chloroform-methanol,acetone-isopropylether, allylalcohol-allylether,allylalcohol-cyclohexane, butanol-butylacetate, butanol-1-butylether,ethanol-ethylbutylether, propylacetate-propanol,isopropylether-isopropanol, methanol-ethanol-isopropanol, andethylacetate-ethanol-acetic acid.

EXAMPLES

The following examples are provided to illustrate one or more preferredembodiments of the invention, but are not limited embodiments thereof.Numerous variations can be made to the following examples that liewithin the scope of the invention.

Example 1 Preparation of Polyimide Dense Film Membrane Usingpoly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine) Polyimide(NPI-1)

An aromatic poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine) polyimide (abbreviatedas NPI-1) containing UV cross-linkable sulfonic groups was synthesizedfrom 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride (DSDA) and2,4,6-trimethyl-m-phenylenediamine (TMPDA) in DMAc polar solvent by atwo-step process involving the formation of the poly(amic acid) followedby a solution imidization process. Acetic anhydride was used as thedehydrating agent and pyridine was used as the imidization catalyst forthe solution imidization reaction. For example, a 250 mL three-neckround-bottom flask equipped with a nitrogen inlet and a mechanicalstirrer was charged with 10.5 g of TMPDA and 42 g of DMAc. Once TMPDAwas fully dissolved, 25.8 g of DSDA solid powder was added to thesolution of TMPDA stepwise under stirring in the flask. 50 g ofdimethylacetamide (DMAc) was added to the solution after the TMPDApowder was added. The reaction mixture was mechanically stirred for 24hours at ambient temperature to give a viscous poly(amic acid) solution.Then 14.7 g of acetic anhydride was added slowly to the reaction mixtureunder stirring followed by the addition of 22.8 g of pyridine to thereaction mixture. The reaction mixture was mechanically stirred for anadditional 2.0 hours at 90° C. to yield a polyimide designated as NPI-1for the purpose of this application. The NPI-1 product in a fine fiberform was recovered by slowly precipitating the reaction mixture into alarge amount of methanol and acetone mixture with 1:1 volume ratio. Theresultant NPI-1 polyimide fibers were then thoroughly rinsed withmethanol and dried in a vacuum oven at 100° C. for 24 hours.

The NPI-1 polymer dense film membrane was prepared as follows: 12.0 g ofNPI-1 polyimide was dissolved in a solvent mixture of 19.5 g of NMP and13.7 g of 1,3-dioxolane. The mixture was mechanically stirred for 2hours to form a homogeneous casting dope. The resulting homogeneouscasting dope was filtered and allowed to degas overnight. The NPI-1polymer dense film membrane was prepared from the bubble free castingdope on a clean glass plate using a doctor knife with a 20-mil gap. Themembrane together with the glass plate was then put into a vacuum oven.The solvents were removed by slowly increasing the vacuum and thetemperature of the vacuum oven. Finally, the membrane was dried at 200°C. under vacuum for at least 48 hours to completely remove the residualsolvents to form a polymer membrane in dense film.

Example 2

Evaluation of the CO₂/CH₄ and H₂/CH₄ separation performance of NPI-1membrane prepared in Example 1

The NPI-1 membrane in dense film form was tested for CO₂/CH₄ and H₂/CH₄separations at 50° C. under 791 kPa (100 psig) pure gas feed pressure.The results show that the new NPI-1 membrane has intrinsic CO₂permeability of 73.4 Barrers (1 Barrer=10⁻¹⁰ cm³ (STP) cm/cm² s (cm Hg))and single-gas CO₂/CH₄ selectivity of 25.3 at 50° C. under 791 kPa forCO₂/CH₄ separation. This membrane also has intrinsic H₂ permeability of136.6 Barrers and single-gas H₂/CH₄ selectivity of 47.1 at 50° C. under791 kPa for H₂/CH₄ separation.

Example 3 Preparation of NPI-1 Polyimide Hollow Fiber Membrane UsingNPI-1 Polyimide Prepared in Example 1

A hollow fiber spinning dope containing 29.7 g of NPI-1 polyimide fromExample 1, 62.86 g of NMP, 8.48 g of 1,3-dioxolane, 2.51 g ofisopropanol, and 2.51 g of acetone was prepared. The spinning dope wasextruded at a flow rate of 2.6 mL/min through a spinneret at 50° C.spinning temperature. A bore fluid containing 10% by weight of water inNMP was injected to the bore of the fiber at a flow rate of 0.8 mL/minsimultaneously with the extruding of the spinning dope. The nascentfiber traveled through an air gap length of 5 cm at room temperaturewith a humidity of 25%, and then was immersed into a water coagulantbath at 21° C. and wound up at a rate of 8.0 m/min. The water-wet fiberwas annealed in a hot water bath at 85° C. for 30 minutes. The annealedwater-wet fiber was then sequentially exchanged with methanol and hexanefor three times and for 30 minutes each time, followed by drying at 100°C. in an oven for 1 hour to form NPI-1 hollow fiber membrane.

Example 4 Synthesis of poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-3,3′,4,4′-biphenyl tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) (Referred to as NPI-2)

An aromatic polyimide, poly(3,3′,4,4′-diphenylsulfone tetracarboxylicdianhydride-3,3′,4,4′-biphenyl tetracarboxylicdianhydride-2,4,6-trimethyl-m-phenylenediamine-3,3′,5,5′-tetramethyl-4,4′-methylenedianiline) (referred to as NPI-2) containing UV cross-linkable sulfonicgroups, was synthesized by polycondensation reaction of DSDA and3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) with3,3′,5,5′-tetramethyl-4,4′-methylene dianiline (TMMDA) and TMPDA(DSDA:BPDA:TMMDA:TMPDA=3.06:1.02:2.00:2.00 (molar ratio)) in DMAc polarsolvent. A 500 mL three-neck round-bottom flask equipped with a nitrogeninlet and a mechanical stirrer was charged with 17.8 g of TMMDA, 10.5 gof TMPDA, and 60 g of DMAc. Once TMMDA and TMPDA were fully dissolved,38.3 g of DSDA and 10.5 g of BPDA solid powder was added to the solutionof TMMDA and TMPDA stepwise under stirring in the flask. 40 g of DMAcwas added to the solution after the DSDA and BPDA powder was added.Another 30 g of DMAc was added after about 10 min. The reaction mixturewas then heated to 70° C. to completely dissolve the powder. Another 130g of DMAc was added to the reaction mixture after it was heated at 70°C. for 0.5 hour. The reaction mixture was then cooled down to ambienttemperature and was mechanically stirred for 24 hours at ambienttemperature to give a viscous poly(amic acid) solution. Then 31.4 g ofacetic anhydride was added slowly to the reaction mixture under stirringfollowed by the addition of 48.7 g of pyridine to the reaction mixture.The reaction mixture was mechanically stirred for an additional 2 hoursat 90° C. to yield NPI-2. The polyimide NPI-2 product in a fine fiberform was recovered by slowly precipitating the reaction mixture into alarge amount of methanol. The resultant polyimide NPI-2 fibers were thenthoroughly rinsed with methanol and dried in a vacuum oven at 100° C.for 24 hours.

Example 5 Preparation of NPI-2 Dense Film Membrane

The NPI-2 dense film membrane was prepared as follows: 7.0 g ofpolyimide NPI-2 was dissolved in a solvent mixture of 15.5 g of NMP and12.5 g of 1,3-dioxolane. The mixture was mechanically stirred for 2hours to form a homogeneous casting dope. The resulting homogeneouscasting dope was filtered and allowed to degas overnight. The NPI-2dense film membrane was prepared from the bubble free casting dope on aclean glass plate using a doctor knife with a 20-mil gap. The dense filmtogether with the glass plate was then put into a vacuum oven. Thesolvents were removed by slowly increasing the vacuum and thetemperature of the vacuum oven. Finally, the dense film was dried at200° C. under vacuum for at least 48 hours to completely remove theresidual solvents to form NPI-2 dense film membrane.

Example 6 Preparation of UV Cross-Linked NPI-2 Dense Film Membrane

The NPI-2 dense film membrane prepared in Example 5 was further UVcross-linked by exposure to UV radiation using 254 nm wavelength UVlight generated from a UV lamp with 1.9 cm (0.75 inch) distance fromNPI-3 dense film membrane surface to the UV lamp and a radiation time of10 min at 50° C. The UV lamp described here is a low pressure, mercuryarc immersion UV quartz 12 watt lamp with 12 watt power supply from AceGlass Incorporated.

Example 7 Synthesis of poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromellitic dianhydride-2,4,6-trimethyl-m-phenylenediamine)(Referred to as NPI-3)

An aromatic polyimide, poly(3,3′,4,4′-benzophenone tetracarboxylicdianhydride-pyromellitic dianhydride-2,4,6-trimethyl-m-phenylenediamine)(referred to as NPI-3) containing UV cross-linkable carbonyl groups, wassynthesized by polycondensation reaction of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA)with TMPDA (BTDA:PMDA:TMPDA=2.04:2.04:4.00 (molar ratio)) in NMP polarsolvent. The synthesis procedure for NPI-3 was the same as thatdescribed in Example 4 for NPI-2 except different monomers and solventwere used for the synthesis of NPI-3.

Example 8 Preparation of NPI-3 Dense Film Membrane

The NPI-3 dense film membrane was prepared using a similar procedure asdescribed in Example 5 except the polymer used for making the dense filmmembrane is NPI-3.

Example 9 Preparation of UV Cross-Linked NPI-3 Dense Film Membrane

The NPI-3 dense film membrane prepared in Example 8 was further UVcross-linked by exposure to UV radiation using 254 nm wavelength UVlight generated from a UV lamp with 1.9 cm (0.75 inch) distance fromNPI-3 dense film surface to the UV lamp and a radiation time of 10 minat 50° C. The UV lamp described here is a low pressure, mercury arcimmersion UV quartz 12 watt lamp with 12 watt power supply from AceGlass Incorporated.

Example 10 CO₂/CH₄ and H₂/CH₄ Separation Properties of Dense FilmMembranes

The permeabilities of CO₂, H₂, and CH₄ (P_(CO2), P_(H2), and P_(CH4))and selectivity of CO₂/CH₄ (α_(CO2/CH4)) and H₂/CH₄ (α_(H2/CH4)) of thedense film membranes prepared in Examples 5, 6, 8 and 9, respectively,were measured by pure gas measurements at 50° C. under about 790 kPa(100 psig) pressure. The results are shown in Table 1.

TABLE 1 Pure gas permeation test results of dense film membranes forCO₂/CH₄ and H₂/CH₄ separations ^(a) P_(CO2) P_(H2) Dense film (Barrer)α_(CO2/CH4) (Barrer) α_(H2/CH4) NPI-2 57.5 20.2 109.9 38.6 NPI-2-UVtreated 22.5 38.8 99.0 171 NPI-3 179.0 15.8 256.5 22.7 NPI-3-UV treated64.1 39.8 224.1 139.2 ^(a) Tested at 50° C. under 790 kPa (100 psig)pure gas pressure; 1 Barrer = 10⁻¹⁰ (cm³(STP) · cm)/(cm² · sec · cmHg)

Example 11 Preparation of NPI-2 Hollow Fiber Membranes

A polymer dope consisting of 52.1 g n-methylpyrrolidinone (NMP), 7.0 g1,3-dioxolane, 2.1 g 2-propanol, 2.1 g acetone, and 23.4 g of NPI-2polyimide synthesized in Example 4 was mixed until uniform. Theviscosity of this dope was approximately 280,000 cP at 30° C. This dopewas extruded from the annulus of a hollow fiber membrane spinneret at aflow rate ranging from 0.7 to 3.0 mL/min. At the same time, a boresolution of 10 wt % H₂O/90 wt % NMP flowed from the inner passage of thespinneret at 0.4 to 0.8 mL/min to keep the nascent fiber from collapsingon itself. During extrusion, the dope and spinneret were controlled at50° C. The nascent fiber passed through an air gap of 3 to 10 cm andthen entered a water coagulation bath at approximately 4° C. to allowliquid-liquid demixing and formation of the asymmetric porous portion ofthe hollow fiber membrane. Finally, the solidified hollow fiber membranewas wound on a take-up drum partially submersed in room temperaturewater at 8 to 37 m/min. The resulting NPI-2 hollow fiber membranes had adense selective layer on the outside surface of the fibers.

The newly formed hollow fibers were treated in 85° C. water for 30 minthen soaked in a water bath at room temperature overnight. Then, thefibers were submersed in three successive volumes of methanol for 30 mineach, followed by submersion in three successive volumes of hexane for30 min each. These steps were done to remove residual solvents from thefibers. Next, the fibers were dried for 1 hour at 100° C., and thenbundles of fibers were sealed into modules for gas permeation testing.Details of the specific conditions used for each NPI-2 hollow fibermembrane are shown in Table 2.

Example 12 Preparation of NPI-3 Hollow Fiber Membranes

A polymer dope consisting of 62.6 g NMP, 8.5 g 1,3-dioxolane, 2.5 g2-propanol, 2.5 g acetone, and 24.0 g of NPI-3 polyimide synthesized inExample 7 was mixed until uniform. The viscosity of this dope wasapproximately 300,000 cP at 30° C. This dope was extruded from theannulus of a hollow fiber membrane spinneret at a flow rate ranging from0.7 to 3.0 mL/min. At the same time, a bore solution of 10 wt % H₂O/90wt % NMP flowed from the inner passage of the spinneret at 0.4 to 0.8mL/min to keep the nascent fiber from collapsing on itself. Duringextrusion, the dope and spinneret were controlled at 50° C. The nascentfiber passed through an air gap of 3 to 10 cm and then entered a watercoagulation bath at approximately 3° C. Finally, the solidified hollowfiber membrane was wound on a take-up drum partially submersed in roomtemperature water at 8 to 30 m/min. The resulting membranes had a denseselective layer on the outside surface of the fibers. Details of thespecific conditions used for each of the hollow fiber NPI-3 membranesare shown in Table 3.

A second polymer dope consisting of 70.5 g NMP, 3.5 g 2-propanol, 1.2 glactic acid, and 22.5 g of NPI-3 synthesized in Example 7 was mixeduntil uniform. The viscosity of this dope was approximately 210,000 cPat 30° C. This dope was extruded from the annulus of a hollow fibermembrane spinneret at a flow rate ranging from 0.7 to 3.0 mL/min. At thesame time, a bore solution of 10 wt % H₂O/90 wt % NMP flowed from theinner passage of the spinneret at 0.4 to 0.8 mL/min to keep the nascentfiber from collapsing on itself. During extrusion, the dope andspinneret were controlled at 50° C. The nascent fiber passed through anair gap of 3 to 10 cm and then entered a water coagulation bath atapproximately 5° C. Finally, the solidified hollow fiber membrane waswound on a take-up drum partially submersed in room temperature water at8 to 37 m/min. The resulting NPI-3 hollow fiber membranes had a denseselective layer on the outside surface of the fibers. Details of thespecific conditions used for each of the hollow fiber membranes areshown in Table 4.

The newly formed hollow fibers from each set of membranes were treatedin 85° C. water for 30 min then soaked in a water bath at roomtemperature overnight. Then, the fibers were submersed in threesuccessive volumes of methanol for 30 min each, followed by submersionin three successive volumes of hexane for 30 min each. Next, the fiberswere dried for 1 hour at 100° C., and then bundles of fibers were sealedinto modules for gas permeation testing.

Example 13

CO₂/CH₄ Separation Properties of NPI-2 Polyimide Hollow Fiber Membranes

The polyimide hollow fiber membranes prepared from NPI-2 polyimide inExample 11 were tested for single-gas permeation of CO₂ and CH₄ at 50°C. with the feed at 790 kPa (100 psig) and the permeate at approximately101 kPa (0 psig). Performance of these membranes is shown in Table 2along with the unique fabrication conditions for each membrane. Otherfabrication conditions for these membranes were described in Example 11.All of the NPI-2 polyimide hollow fiber membranes shown in Table 2 werenearly defect-free and had CO₂/CH₄ selectivities near to or higher thanthe intrinsic selectivity of the NPI-2 dense film membrane.

TABLE 2 Single-gas CO₂/CH₄ permeation performance of NPI-2 hollow fibermembranes. Air Dope Bore Take-up Single gas Membrane gap rate rate rateP_(CO2)/L # (cm) (mL/min) (mL/min) (m/min) (A.U.) α_(CO2/CH4) 1 10 0.70.4 8.0 21.2 38.6 2 5 0.7 0.4 8.0 16.6 22.8 3 10 2.6 0.8 23.5 33.5 27.94 7 2.6 0.8 23.5 31.8 25.7 5 3 2.6 0.8 23.5 30.2 15.3 6 10 3.0 0.6 23.522.5 34.4 7 7 3.0 0.6 23.5 22.3 23.8 8 7 3.0 0.6 30.2 24.0 26.9 9 7 3.00.6 36.9 26.2 26.4 10 3 3.0 0.6 23.5 33.9 20.9 11 3 3.0 0.6 23.5 33.920.9 (1 A.U. = 1 ft³ (STP)/h · ft² · 100 psi)

Example 14 CO₂/CH₄ Separation Properties of NPI-3 Hollow Fiber Membranes

The polyimide hollow fiber membranes prepared from NPI-3 in Example 12were tested for single-gas permeation of CO₂ and CH₄ at 50° C. with thefeed at 790 kPa (100 psig) and the permeate at approximately 101 kPa (0psig). Two different sets of NPI-3 hollow fiber membranes were preparedusing different dope formulations, as described in Example 12.Performance of these membranes is shown in Tables 3 and 4 along with theunique fabrication conditions for each membrane. Other fabricationconditions for these membranes were described in Example 12. All of thepolyimide NPI-3 hollow fiber membranes shown in Tables 3 and 4 werenearly defect-free and had CO₂/CH₄ selectivities higher than theintrinsic selectivity of the NPI-2 hollow fiber membranes.

TABLE 3 Single-gas CO₂/CH₄ permeation performance of NPI-3 hollow fibermembranes prepared using a dope consisting of 62.6 g NMP, 8.5 g1,3-dioxolane, 2.5 g 2-propanol, 2.5 g acetone, and 24.0 g of NPI-3polyimide. Air Dope Bore Take-up Single gas Membrane gap rate rate rateP_(CO2)/L # (cm) (mL/min) (mL/min) (m/min) (A.U.) α_(CO2/CH4) 12 10 0.70.4 8.0 8.8 35.8 13 10 2.6 0.8 23.5 15.5 29.7 14 7 2.6 0.8 23.5 15.821.6 15 3 2.6 0.8 23.5 20.5 30.5 16 7 3.0 0.6 23.5 16.4 27.2 17 7 3.00.6 30.2 19.8 21.4 18 3 3.0 0.6 23.5 17.2 20.7 (1 A.U. = 1 ft³ (STP)/h ·ft² · 100 psi)

TABLE 4 Single-gas CO₂/CH₄ permeation performance of NPI-3 hollow fibermembranes prepared using a dope consisting of 70.5 g NMP, 3.5 g2-propanol, 1.2 g lactic acid, and 22.5 g of NPI-3. Air Dope BoreTake-up Single gas Membrane gap rate rate rate P_(CO2)/L # (cm) (mL/min)(mL/min) (m/min) (A.U.) α_(CO2/CH4) 19 10 0.7 0.4 8.0 17.3 25.1 20 102.6 0.8 23.5 21.3 26.1 21 7 2.6 0.8 23.5 20.4 25.1 22 10 3.0 0.6 23.523.3 21.3 23 7 3.0 0.6 23.5 20.9 22.7 24 7 3.0 0.6 30.2 17.3 30.0 25 33.0 0.6 23.5 23.5 23.6 (1 A.U. = 1 ft³ (STP)/h · ft² · 100 psi)

Example 15 Preparation of Blend Dense Film Membrane of NPI-2/PES

A blend polymer dense film membrane of NPI-2 polyimide andpolyethersulfone (PES) was prepared as follows: 3.5 g of polyimide NPI-2and 3.5 g of PES were dissolved in a solvent mixture of 15.5 g of NMPand 12.5 g of 1,3-dioxolane. The mixture was mechanically stirred for 2hours to form a homogeneous casting dope. The resulting homogeneouscasting dope was filtered and allowed to degas overnight. The NPI-2/PESblend dense film membrane was prepared from the bubble free casting dopeon a clean glass plate using a doctor knife with a 20-mil gap. The densefilm together with the glass plate was then put into a vacuum oven. Thesolvents were removed by slowly increasing the vacuum and thetemperature of the vacuum oven. Finally, the dense film was dried at200° C. under vacuum for at least 48 hours to completely remove theresidual solvents to form NPI-2/PES blend dense film membrane.

1. A process for separating at least one gas from a mixture of gases,the process comprising: a) providing a polyimide gas separation membranecomprising an aromatic polyimide polymer that comprises a plurality offirst repeating units of formula (I)

wherein X1 is selected from the group consisting of

and mixtures thereof; X2 is selected from the group consisting of

and mixtures, wherein Y is selected from the group consisting of

and mixtures thereof and wherein n and m are independent integers from 2to 500; b) contacting the mixture to one side of said polyimide gasseparation membrane to cause said at least one gas to permeate the saidpolyimide gas separation membrane; and c) removing from an opposite sideof the said polyimide gas separation membrane a permeate gas compositioncomprising a portion of said at least one gas which permeated saidmembrane.
 2. The process of claim 1 wherein said X2 is selected from thegroup consisting of

and mixtures thereof.
 3. The process of claim 1 wherein said X2 isselected from the group consisting of

and mixtures thereof.
 4. The process of claim 1 wherein said Y isselected from the group consisting of

and mixtures thereof.
 5. The process of claim 1 wherein said Y isselected from the group consisting of

and mixtures thereof.
 6. The process of claim 1 wherein said Y isselected from the group consisting of

and mixtures thereof.
 7. The process of claim 1 wherein said X2 isselected from the group consisting of

and mixtures thereof and wherein Y is selected from the group consistingof

and mixtures thereof.
 8. The process of claim 1 wherein said X2 isselected from the group consisting of

and mixtures thereof and wherein Y is selected from the group consistingof

and mixtures thereof.
 9. The process of claim 1 wherein said X1 is

and wherein X2 is selected from the group consisting of

and mixtures thereof, and wherein Y is selected from the groupconsisting of

and mixtures thereof.
 10. The process of claim 1 wherein said X1 is

and wherein X2 is selected from the group consisting of

and mixtures thereof, and wherein Y is selected from the groupconsisting of

and mixtures thereof.
 11. The process of claim 1 wherein said mixture ofgases comprises a mixture of one or more volatile organic compounds andatmospheric gases.
 12. The process of claim 1 wherein said mixture ofgases comprises a mixture of hydrogen and nitrogen.
 13. The process ofclaim 1 wherein said mixture of gases comprises a mixture of at leastone gas selected from carbon dioxide and hydrogen sulfide that is mixedwith methane.
 14. The process of claim 1 wherein said mixture of gasescomprises a mixture of carbon dioxide and nitrogen.
 15. The process ofclaim 1 wherein said mixture of gases comprises a mixture of hydrogenand methane.
 16. The process of claim 1 wherein said mixture of gasescomprises a mixture of olefins and paraffins.
 17. The process of claim 1wherein said mixture of gases comprises a mixture of iso and normalparaffins.